Synthesis and crystal structures of the phosphoraneiminato complexes [SbF2(NPEt(3))](2) and [SbF(NPEt(3))(2)](2) as well as of NMe(4)(+)SbF(4)(-)

The title compounds have been prepared from antimony trifluoride with the silylated phosphaneimine Me(3)SiNPEt(3) and [NMe(4)]F, respectively. They were characterized by IR spectroscopy and by crystal structure determinations. [SbF2(NPEt(3))](2): Space group Pbca, Z = 8, structure determination with 1264 unique reflections, R(1) = 0.028 for reflections with I > 2 sigma(I). Lattice dimensions at -80 degrees C: a = 1284.8, b = 1162.4, c = 1380.4 pm. The compound forms centrosymmetric dimeric molecules, in which the psi-trigonal-bipyramidal coordinated antimony atoms are linked via mu(2)-N bridges of the NPEt(3)(-) ligands. [SbF(NPEt(3))(2)](2): Space group P2(1)/c, Z = 4, structure determination with 2270 unique reflections, R(1) = 0.029 for reflections with I > 2 sigma(I). Lattice dimensions at -75 degrees C: a = 815.8, b = 1121.2, c = 2068.5 pm, beta = 101.09 degrees. The compound forms centrosymmetric dimeric molecules, in which the psi-trigonal-bipyramidal coordinated antimony atoms are linked via mu(2)-N bridges of one of the two NPEt(3)(-) ligands. The other NPEt(3)(-) group is terminally connected. NMe(4)(+)SbF(4)(-): Space group P2(1)/c, Z = 4, structure determination with 1503 unique reflections, R(1) = 0.069 for reflections with I > 2 sigma(I). Lattice dimensions at -50 degrees C: a = 539.80, b = 896.10, c = 1760.3 pm, beta = 90.338 degrees. The compound includes monomeric SbF4- ions with distorted psi-trigonal-bipyramidal environment of the antimony atoms.